JPH04359049A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition, excellent in impact resistance and molding fluidity and suitable as various automotive parts, mechanical parts, etc. CONSTITUTION:A thermoplastic resin composition is obtained by blending (A) 100 pts.wt. resin composition composed of (A1) 10-90wt.% polyarylate composed of a dihydric phenol (derivative) expressed by formula I (X is O, S, SO2, etc.; R1 to R4 and R1' to R4' are H, halogen or 1-4C hydrocarbon) and an aromatic dicarboxylic acid (derivative) and (A2) 90-10wt.% polyalkylene phenylene ester (e.g. polyethylene terephthalate) with (B) 1-50 pts.wt., preferably 3-30 pts.wt. modified polyolefinic copolymer having one structural unit having 21 amide groups, glycidyloxy groups or glycidyl groups based on 4-5000 carbon atoms of a polyolefin and one structural unit having glycidyl ether group expressed by formula II (Ar is 6-23C aromatic hydrocarbon having glycidyloxy group; R is H or methyl).

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a new thermoplastic resin composition that provides molded articles with excellent impact resistance and heat distortion temperature, as well as excellent fluidity during molding.

0002

BACKGROUND OF THE INVENTION Resin compositions comprising polyarylate and polyalkylene phenylene ester are well known and can provide molding materials with an excellent balance between heat deformation resistance and chemical resistance. However, the impact resistance of this composition is generally low, which poses a practical problem. In order to solve this problem, JP-A No. 61-26657 discloses that a glycidyl ester group-containing copolymer consisting of an α-olefin and a glycidyl ester of an α,β-unsaturated acid is added to the composition. A method is disclosed. However, although this method does improve the notched Izod impact strength at room temperature, it hardly improves the notched Izod impact strength at low temperatures (-30°C), and the molding fluidity significantly decreases. This has serious practical problems.

0003

[Problems to be Solved by the Invention] The present invention provides impact resistance,
In particular, the present invention provides a resin composition that has outstanding Izod impact strength at low temperatures and does not reduce molding fluidity.

0004

[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors have discovered a novel resin composition comprising polyarylate, polyalkylene phenylene ester, and a specific modified polyolefin copolymer. The present invention was achieved by discovering that impact resistance, particularly low-temperature Izod impact strength, can be significantly improved without reducing molding fluidity. That is, the present invention uses the following component (A) 100
The content of the resin composition is 1 to 50 parts by weight of component (B) below. (A) (A) The following general formula (I)

[0005]

[C4]

(wherein, X is O, S, SO2, CO,
selected from the group consisting of C1 to C20 alkylene groups and C6 to C20 alkylidene groups, R1 , R2
, R3, R4, R1', R2', R3', and R4'
is selected from the group consisting of a hydrogen atom, a halogen atom, and a C1 to C4 hydrocarbon group), or a derivative thereof, and an aromatic dicarboxylic acid or a derivative thereof, 10 to 90% by weight of a polyarylate. (b) a resin composition consisting of 90 to 10% by weight of polyalkylene phenylene ester; (B) at least one amide group and at least one glycidyloxy group or glycidyl group per 4 to 5,000 carbon atoms of the polyolefin; A modified polyolefin copolymer having one structural unit.

[0007] The resin composition (A) used in the present invention is
Consists of polyarylate (a) and polyalkylene phenylene ester (b). The polyarylate (a) used in the present invention is synthesized, for example, by polycondensation reaction of dihydric phenols or derivatives thereof and aromatic dicarboxylic acids or derivatives thereof. As the dihydric phenols used in the present invention, general formula (I)

[0008]

[C5]

(X in the formula is O, S, SO2, CO,
selected from the group consisting of C1 to C20 alkylene groups and C6 to C20 alkylidene groups, R1 , R2 ,
R3, R4, R1', R2', R3', and R4'
is selected from the group consisting of a hydrogen atom, a halogen atom, and a C1 to C4 hydrocarbon group). For example, 2,2-bis(4'-
hydroxyphenyl)propane (also known as bisphenol A)
), bis(4-hydroxyphenyl)methane, bis(4
-hydroxy-3,5-dimethylphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, 1,1-bis(4'-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)cyclohexylmethane, 1,1-bis(4'-hydroxyphenyl)-1-
Phenylethane, 4,4'-dihydroxydiphenyl ether, bis(4-hydroxy-3,5-dimethylphenyl) ether, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxy-3,5-dimethylphenyl)sulfone, Examples include 4,4'-dihydroxybenzophenone and 2,2-bis(4'-hydroxy-3',5'-dimethylphenyl)propane. Further, examples of the derivatives of the dihydric phenols include their alkali metal salts, diacetates, and the like. The above dihydric phenols and their derivatives may be used alone or in combination of two or more. Furthermore, if necessary, a small amount of a divalent compound such as 4',4-biphenol, hydroquinone, resorcinol, or 2,6-dihydroxynaphthalene may be used in combination with the dihydric phenols or derivatives thereof.

Various aromatic dicarboxylic acids can be used in the present invention. For example, isophthalic acid, terephthalic acid, diphenyl ether-4,
Examples include 4'-dicarboxylic acid, benzophenone-4,4-dicarboxylic acid, and naphthalene-2,6-dicarboxylic acid. Among the above aromatic dicarboxylic acids, especially isophthalic acid,
Terephthalic acid is preferred. Furthermore, examples of derivatives of aromatic dicarboxylic acids include dichlorides, alkylated products, and arylated products thereof. The above aromatic dicarboxylic acids and derivatives thereof may be used alone or in combination of two or more.

The polyarylate used in the present invention can be produced using various polymerization methods such as interfacial polycondensation, solution polymerization, and melt polymerization. However, the solution viscosity is 0.2 to 1.5 in terms of intrinsic viscosity (chloroform solution, 30°C)
Preferably, the range is . Those outside this range tend to have poor impact resistance, heat deformation resistance, moldability, etc.

The polyalkylene phenylene ester (b) used in the present invention can be produced by any method such as an interfacial polymerization method, a solution polymerization method, or a melt polymerization method. The polyalkylene phenylene ester used in the present invention has the following general formula (
IV)

[0013]

[C6]

It is expressed as follows. Here, R1,
R2, R3, R4 are hydrogen atoms, alkyl groups, alkoxy groups, alkyl ester groups, cyano groups, amino groups,
It is selected from a sulfone group, a nitro group, a phenoxy group, and the like. m is an integer from 1 to 10. Specific examples of the polyester used in the present invention include polyethylene terephthalate, polyethylene isophthalate, polytrimethylene terephthalate, polytrimethylene isophthalate, polybutylene terephthalate, polybutylene isophthalate, etc., which may be used alone or in combination of two or more. It is used as Among them, polyethylene terephthalate (PET), polybutylene terephthalate (PBT)
) is preferred. In addition, the intrinsic viscosity of these polyalkylene phenylene esters is 0.3 to 1.5 dl/g [phenol/tetrachloroethane = 6/4 (weight ratio), 25
℃], particularly 0.4 to 1.2
It is preferably in the range of dl/g. Intrinsic viscosity is 0.
If it is less than 3 dl/g, sufficient impact strength cannot be obtained,
Moreover, if it exceeds 1.5 dl/g, molding fluidity tends to decrease, which is not preferable.

The modified polyolefin copolymer (B) used in the present invention is a polyolefin having 4 to 50 carbon atoms.
It is a modified polyolefin copolymer having one structural unit having at least one amide group and at least one glycidyloxy group or glycidyl group per 00 carbon atoms, and in particular, per 4 to 5000 carbon atoms of the polyolefin. , the following general formula (II)

[0016]

[C7]

[0017] A glycidyl ether group represented by It is preferable to use one structural unit having one structural unit.

[0018] The polyolefin used in the present invention is:
Homopolymers of olefins such as polyethylene, polypropylene, and polybutene-1, or ethylene-propylene copolymers, ethylene-propylene-diene copolymers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid ester copolymers, etc. These may be used alone or in combination of two or more. Particularly preferred are ethylene-propylene copolymers and ethylene-propylene-diene copolymers. Examples of the diene include conjugated dienes such as butadiene, isoprene, chloroprene, and phenylpropadiene, cyclopentadiene, 1,5-norbonanodiene, and 1,3
-cyclohexadiene, 1,4-cyclohexadiene,
Examples include cyclic dienes such as 1,5-cyclooctadiene and 1,3-cyclooctadiene, and α,ω-nonconjugated dienes, which may be used alone or in combination of two or more. In addition, in smaller amounts, unsaturated monomers copolymerizable with the above copolymers, such as vinyl ethers, vinyl esters such as vinyl acetate and vinyl propionate, acrylic acids and methacrylic acids such as methyl, ethyl, propyl, butyl, etc. One or more types of acid esters, acrylonitrile, styrene, etc. may be copolymerized. General formula (II) above
The structural unit having a glycidyl ether group represented by the following general formula (V)

[0019]

[Chemical formula 8]

(wherein, Ar represents an aromatic hydrocarbon group having 6 to 23 carbon atoms and has at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group) having a glycidyl ether group. The modifier is introduced into the polyolefin by radical addition or copolymerization. Such a modifier is disclosed in Japanese Patent Publication No. 2-0515.
It can be manufactured by the method described in Japanese Patent No. 50. Among the above modifiers, specifically, for example, the following formula (V
I)

[0021]

[Chemical formula 9]

Compounds shown below can be preferably used. Modified polyolefin copolymer (B
) must contain one structural unit having at least one amide group and at least one glycidyloxy group or glycidyl group per 4 to 5,000 carbon atoms, preferably 50 to 3,000 carbon atoms in the polyolefin. More preferably, it is necessary to contain one structural unit having a glycidyl ether group represented by the above general formula (II). Outside the above range, the impact improving effect may not be sufficient or the fluidity during molding may be reduced, which is disadvantageous. Preferred examples of the modified polyolefin copolymer include ethylene-propylene copolymer or ethylene-propylene copolymer.
The propylene-diene copolymer has the following structural formula (III)

[0023]

[Chemical formula 10]

A structural unit having a glycidyl ether group represented by the following formula is grafted. On the other hand, the melt index of the modified polyolefin copolymer (B) (
MI) is usually preferably in the range of 0.01 to 100. If it is outside the above range, the effect of improving impact resistance tends to be insufficient, which is not preferable. Here, the melt index is a value measured according to ASTM D-1238 (measured at 230°C), and the unit is g/10 minutes.

[0025] The above modified polyolefin copolymer (B)
There are no particular restrictions on the manufacturing method, but the polyolefin and the above-mentioned modifier may be mixed using an extruder, hot roll, Brabender,
A method of melt-mixing using various blenders such as a Banbury mixer, or a method of melt-mixing the olefin monomer and the modifier using a general polymerization method such as a radical polymerization method, a cationic polymerization method,
Copolymerization can also be carried out by anionic polymerization or coordination polymerization.

Such modified polyolefin copolymer (B
) is added in an amount of 10 to 90% by weight of polyarylate (a).
, polyalkylene phenylene ester (b) 90-10
The amount is 1 to 50 parts by weight, preferably 3 to 30 parts by weight, based on 100 parts by weight of the resin composition (A). If the amount of the modified polyolefin copolymer (B) added is less than 1 part by weight, the effect of impact improvement will not be sufficient;
If it exceeds 0 parts by weight, heat deformation resistance and fluidity during molding will be poor.

The method for producing the thermoplastic resin composition of the present invention is not particularly limited, but it is most preferable to use a melt mixing method, for example, melt mixing using various blenders such as an extruder, hot roll, Brabender, Banbury mixer, etc. do it. If necessary, lubricants such as wax, stabilizers such as phosphorus and phenol, ultraviolet absorbers, pigments, flame retardants, plasticizers, inorganic fillers, reinforcing fibers, etc. may be added to the composition of the present invention. By adding it, new functionality may be separately imparted to the resin composition. The thermoplastic resin composition of the present invention has excellent fluidity during molding, and molded products obtained from the composition have excellent impact resistance and heat distortion temperature, for example,
It can provide a molding material suitable for automobile parts, mechanical parts, electric/electronic equipment parts, etc.

[0028]

[Examples] The present invention will be explained in more detail based on examples below, but the present invention is not limited to these examples, and can be modified as appropriate without changing the gist of the invention. These are also included.

1. Production Examples 1 to 14 of Resin Compositions The following polyarylate, polyalkylene phenylene ester, and modified polyolefin copolymer were blended at the predetermined ratios shown in Table 1, , LABOTEX 30) at a temperature of 270° C. to produce a pellet-shaped resin composition. Polyarylate: bisphenol A, isophthalic acid dichloride and terephthalic acid dichloride (8/2 molar ratio)
A polyarylate (intrinsic viscosity: 0.63) was produced by performing a polycondensation reaction with a mixture consisting of the following at a molar ratio of 1:1.

Polyalkylene phenylene ester: polyethylene terephthalate (manufactured by Kuraray Co., Ltd., Clapet KD226R), polybutylene terephthalate (
General Electric Company, Barox 310)

0
[031] Modified polyolefin copolymer (B-1): Ethylene-propylene-diene copolymer (Nippon Gosei Co., Ltd.) with a melt index of 0.4 g/10 minutes when a load of 2.2 kg is applied at a temperature of 230°C. Rubber Co., Ltd. EP5
7P) For 100 parts by weight, the following formula (VI)

003
2]

[Chemical formula 11]

3 parts by weight of a modifier having a glycidyl ether group represented by the following formula, and 0.0 parts by weight of α,α'-bis(t-butylperoxy-m-isopropyl)benzene (Perbutyl P, manufactured by NOF Corporation). 16 parts by weight was added at room temperature and mixed using a twin screw extruder (Japan Steel Works, TEX44).
extrusion reaction at 250°C. The obtained pellets were crushed and washed five times with methylene chloride to remove unreacted modifier and modifier homopolymer, and the amount of grafted modifier was determined from the IR spectrum and elemental analysis of nitrogen atoms. It was 1.9% by weight. Furthermore, the obtained pellets had a melt index of 0.0 at 230°C.
5 g/10 minutes, the polyolefin had one structural unit having a glycidyl ether group represented by the general formula (II) per 972 carbon atoms.

Modified polyolefin copolymer (B-2)
: Ethylene-propylene-diene copolymer (manufactured by Japan Synthetic Rubber Co., Ltd. E
P57P) to 100 parts by weight, the above structural formula (VI)
6 parts by weight of a modifier having a glycidyl ether group represented by
0.16 parts by weight of benzene (Perbutyl P, manufactured by Nihon Yushi Corporation) was added and mixed at room temperature, and the mixture was extruded and reacted at 250° C. using a twin-screw extruder (TEX44, manufactured by Japan Steel Works). The resulting pellets were crushed and washed five times with methylene chloride to remove unreacted modifier and modifier homopolymer, and the grafted amount of modifier was determined from the IR spectrum and elemental analysis of nitrogen atoms. , 3.8% by weight. Furthermore, the obtained pellets had a melt index of 0.4 g/1 at 230°C.
0 minutes, per 486 carbon atoms of polyolefin, the general formula (
It had one structural unit having a glycidyl ether group represented by II).

Modified polyolefin copolymer (B-3)
: Ethylene-propylene copolymer with a melt index of 3.2 g/10 minutes when a load of 2.2 kg is applied at a temperature of 230°C (EP02P manufactured by Japan Synthetic Rubber Co., Ltd.)
), 3 parts by weight of a modifier having a glycidyl ether group represented by the above structural formula (VI), and α,α'-bis(t-butylperoxy-m-isopropyl)benzene ( Nippon Oil & Fats Co., Ltd., Perbutyl P)
0.16 parts by weight was added and mixed at room temperature, and the mixture was extruded and reacted at 250°C using a twin-screw extruder (TEX44, manufactured by Japan Steel Works). The resulting pellets were crushed and washed five times with methylene chloride to remove unreacted modifier and modifier homopolymer, and the grafted amount of modifier was determined from the IR spectrum and elemental analysis of nitrogen atoms. , 2.4
% by weight. Furthermore, the obtained pellets had a melt index of 4.3 g/10 min at 230°C and had one structural unit having a glycidyl ether group represented by the general formula (II) per 758 carbon atoms of the polyolefin. Ta.

Modified polyolefin copolymer (B-4)
: Ethylene-propylene copolymer (manufactured by Japan Synthetic Rubber Co., Ltd., EP02) with a melt index of 3.2 g/10 minutes when a load of 2.2 kg is applied at a temperature of 230 ° C.
P) For 100 parts by weight, 6 parts by weight of a modifier having a glycidyl ether group represented by the above structural formula (VI), and further α,α'-bis(t-butylperoxy-m-isopropyl)benzene. (Nippon Oil & Fats Co., Ltd., Perbutyl P
)0.16 parts by weight were added and mixed at room temperature, and the mixture was extruded and reacted at 250°C using a twin-screw extruder (TEX44, manufactured by Japan Steel Works). The obtained pellets were crushed and washed five times with methylene chloride to remove unreacted modifier and modifier homopolymer, and the amount of grafted modifier was determined from the IR spectrum and elemental analysis of nitrogen atoms. ,4.
It was 8% by weight. In addition, the obtained pellets were heated at 230°C.
The polyolefin had a melt index of 3.8 g/10 minutes, and had one structural unit having a glycidyl ether group represented by the general formula (II) per 370 carbon atoms of the polyolefin.

Comparative Examples 1 to 9 The polyarylates, polyalkylene terephthalates, and glycidyl ester group-containing copolymers shown below used in the examples were blended at the predetermined ratios shown in Table 1, and the mixture was heated in a twin-screw extruder ( A resin composition in the form of pellets was prepared by extrusion at a temperature of 270° C. using LABOTEX 30 (manufactured by Japan Steel Works, Ltd.). Glycidyl ester group-containing copolymer (B-5): Ethylene/glycidyl methacrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd., Bondfast E)

2. Measurement of Izod impact strength and spiral flow length The pelletized resin composition prepared in 1 above was heated at 120°C.
After drying under reduced pressure for 15 hours at a temperature of ~9). Izod impact strength measurement method: ASTM D 2
Measured according to the measurement method specified in 56 (1/4
With inch notch, environmental temperature 23℃, -30℃). Spiral flow value: Using a 3.5 oz injection molding machine (manufactured by Toshiba Machine Co., Ltd., IS80EPN), the gate cross section was 3mm x 3
A spiral mold with a width of 4 mm and a thickness of 3 mm was installed, and the flow length was measured.

[0039]

[Table 1]

From Table 1 above, the injection molded products obtained from the resin compositions of the present invention prepared by blending the modified polyolefin copolymers B-1 to B-4 have high Izod impact strength,
In addition, in terms of moldability, the spiral flow length is high and the fluidity is excellent (Examples 1 to 14). In contrast, molded products obtained from compositions consisting only of polyarylate, polyethylene terephthalate, or polybutylene terephthalate (Comparative Examples 1, 2, 3, and 7) had low Izod impact strength, and If the amount added is outside the predetermined range, or the composition containing glycidyl ester group-containing copolymer B-5 cannot satisfy both impact resistance and molding fluidity at the same time (Comparative Example 4) ~6, 8, 9). As described above, it is truly a surprising fact that the composition of the present invention, in which the specific modified olefin copolymer described above is blended with polyarylate or polyalkylene terephthalate, exhibits excellent physical properties.

[0041]

Effects of the Invention As explained in detail above, when the resin composition of the present invention is molded as a plastic molding material by various molding methods such as injection molding, extrusion molding, blow molding, and compression molding, various automobile parts and machinery can be produced. It is possible to obtain plastic molded products with excellent impact resistance and molding fluidity, which are suitable for applications such as parts and electrical/electronic parts.

Claims (10)

[Claims] [Claim 1] A resin composition consisting of 1 to 50 parts by weight of the following component (B) based on 100 parts by weight of the following component (A): (A) (A) The following general formula (I) [Formula 1] (In the formula, X is O, S, SO2, CO, C1 to C2
0 alkylene group, and C6 to C20 alkylidene group, R1 , R2 , R3 , R
4, R1', R2', R3', and R4' are selected from the group consisting of a hydrogen atom, a halogen atom, and a C1 to C4 hydrocarbon group) or a derivative thereof, and an aromatic dicarbonate. (b) a resin composition consisting of 90 to 10% by weight of polyalkylene phenylene ester; (B) an amide group per 4 to 5,000 carbon atoms of the polyolefin; and a modified polyolefin copolymer having one structural unit each having at least one glycidyloxy group or glycidyl group. 2. The modified polyolefin copolymer has the following general formula (II) per 4 to 5,000 carbon atoms of the polyolefin: [Formula 2] (where Ar is a carbon number having at least one glycidyloxy group) 2. The modified polyolefin copolymer has one structural unit having a glycidyl ether group represented by 6 to 23 aromatic hydrocarbon groups, and R represents a hydrogen atom or a methyl group. thermoplastic composition. 3. The polyolefin is a copolymer of ethylene and one or more monoolefins having 3 to 16 carbon atoms, or a copolymer of ethylene and one or more monoolefins having 3 to 16 carbon atoms.
The thermoplastic resin composition according to claim 1 or 2, which is a copolymer consisting of one or more polyenes and one or more polyenes. 4. The thermoplastic resin composition according to claim 1, wherein the polyolefin is an ethylene-propylene copolymer. 5. The thermoplastic resin composition according to claim 1, wherein the polyolefin is an ethylene-propylene-diene copolymer. 6. The thermoplastic resin composition according to claim 1, wherein the structural unit having a glycidyl ether group represented by the general formula (II) is grafted to the polyolefin. 7. The thermoplastic resin composition according to claim 1, wherein the structural unit having a glycidyl ether group represented by the general formula (II) is randomly copolymerized with the polyolefin. 8. The thermoplastic resin composition according to claim 1, wherein the structural unit having a glycidyl ether group is represented by the following formula (III). 9. The thermoplastic resin composition according to claim 1, wherein the polyalkylene phenylene ester is polyethylene terephthalate. 10. The thermoplastic resin composition according to claim 1, wherein the polyalkylene phenylene ester is polybutylene terephthalate.